JPH05320694A - Contaminant removing composition and its preparation - Google Patents

Abstract

PURPOSE:To obtain an excellent contaminant removing compsn. which can be simply applied in a wide variety of uses by mixing a terpene hydrocarbon, a water-soluble polysaccharide, a surfactant, a water-soluble alkali (earth) metal salt, and water to thicken the compsn. CONSTITUTION:20-60 pts.wt. terpene hydrocarbon represented by the molecular formula: C10H16 and having 2 non-conjugated double bonds is dispersed in water or a water-polyol mixture in the presence of 0.5-0.03 pts.wt. surfactant. The resulting dispersion is added to a soln. of 0.5-5.0 pts.wt. water-soluble polysaccharide in water or a water-polyol mixture. The resulting mixture is allowed to thicken or gel in the presence of 0.01-3.00 pts.wt. (in terms of a metal oxide) water-soluble alkali metal salt or alkaline earth metal salt to obtain the desired compsn., which is a novel commercialized compsn. in the form of a viscous liq., a sol or a solid for use in removal of a variety of contaminants such as oil-based inks, oils, gums, and adhesives.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for removing contaminants and a method for producing the same, more specifically, oil-based inks, oil-based paints, edible oils, machine oils, tars, pitches, gums,
Regarding the composition capable of effectively removing grease, adhesive residue, asphalt, filth of birds and animals, food juice / residue and various stains, plastics industry, leather industry,
In addition to being useful in the metal industry, ceramics industry, textile industry, vehicle industry, printing industry, construction and civil engineering industry,
It is also conveniently used as daily necessities, office supplies, hospital supplies, etc.

[0002]

2. Description of the Related Art Conventionally, as a substance for removing contaminants, as a solution type substance, thinner, freons, trihaloethane, trichlene, perklene, an aqueous solution containing a surfactant and the like have been used. Uses soap, powder detergent or sand.

As an intermediate product between the solution type and the solid type, a liquid detergent, shampoo or polishing sand containing a surfactant,
Soft soaps, pastes containing surfactants, etc. are known. These usages are roughly classified into oil-based pollutants and water-based pollutants, and if the usages are incorrect, the effects are diminished and the purpose is often not achieved.

[0004]

SUMMARY OF THE INVENTION Here, the inventors of the present invention can adapt to a wide range of applications and can easily use a composition for removing contaminants, for example, which can be easily used for commonly used oil-based inks and adhesives. We know that it is important to research the production method and to elucidate the physical properties of a new ultrafine dispersion system: the micelle state of the surfactant in the aqueous liquid and the stable dispersion of the organic solvent in this micelle region. It was

[0005]

Means for Solving the Problems The present inventors have conducted a number of experiments and found that a specific terpene hydrocarbon, that is, a compound having an appropriate cyclohexene ring, is used as the organic solvent in view of physical and safety. Is also the most suitable,
Moreover, it was clarified that the water-soluble polysaccharide having a pyranose ring in the molecule is the most suitable as the dispersing polymer that interacts with the terpene hydrocarbon.

As a result of further research based on the above new facts, the present inventors have found that 20 to 60 terpene hydrocarbons having two non-conjugated double bonds whose composition formula is represented by C ₁₀ H _16.
Parts by weight, water-soluble polysaccharide 0.5 to 5.0 parts by weight, surfactant 0.5 to 30.0 parts by weight, water-soluble inorganic salt 0.01 to 3.00 parts by weight and water or water-polyol mixture. It has been found that a composition consisting of 30 to 70 parts by weight is a very excellent composition for removing contaminants.

Further, a terpene hydrocarbon having two non-conjugated double bonds represented by the composition formula C ₁₀ H ₁₆ is 20 to 60.
Parts by weight in water or a water-polyol mixture in the presence of 0.5 to 30.0 parts by weight of a surfactant, and then water or 0.5 to 5.0 parts by weight of water-soluble polysaccharide. In the presence of 0.01 to 3.00 parts by weight of a water-soluble inorganic salt in addition to a solution of a water-polyol mixture, an extremely good quality contaminant-removing composition can be obtained when thickening or gelling. Revealed.

[0008]

[Structure and Action of the Invention] The terpene hydrocarbon represented by the composition formula C ₁₀ H ₁₆ has two double bonds contained in the molecule in a conjugated state and in a non-conjugated state. There are some cases. Conjugated terpene-based hydrocarbons have a slightly higher dissolving power than non-conjugated ones, but on the other hand, they have too great an affinity for water etc. and are rather problematic in their transfer / removal properties to pollutants. Was given.

For example, as the conjugated terpene hydrocarbon represented by the composition formula C ₁₀ H ₁₆ , myrcene, alloocimene,
There are α-terpinene, α-ferrandrene, γ-ferrandrene, menogen, etc., but rather than these, the non-conjugated terpene hydrocarbons referred to in the present invention, such as limonene, dipentene, β-terpinene, γ-terpinene, Although isolimonene, terpinolene, carbestrene, sylvestrene, etc. have a slightly weak affinity for water, etc., they have good transferability to and solubility in contaminants in aqueous micelles. Was found to be preferable.

The water-soluble polysaccharides used in the present invention include dextrin, cationized starch, alginic acid or a salt thereof, carrageenan, gellan gum, locust bean gum, guar gum, gum arabic, tragacanth gum, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxy. Methylcellulose or its salt, carboxymethylstarch or its salt, glucomannan, zaleptmannan, plant (Trolloiye, seaweed, troloy, gambir, leeks, pepper, bracken, tabuki, orange endothelium, etc.)
It is selected from mucus and is often used alone or as a mixture of two or more.

Instead of this water-soluble polysaccharide, a water-soluble polymer containing no pyranose ring, such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid,
Polymethacrylic acid, hydroxyethyl acrylate polymer, hydroxypropyl acrylate, ethylene
Water-soluble polymers such as alkali salts of acrylic acid copolymers, sodium polyacrylate, polyacrylamide, polyethyleneimine, methylolated nylon, casein, polyethylene oxide, polypropylene oxide and water-soluble polyesters are terpene-based compounds referred to in the present invention. The affinity for hydrocarbons is too great and the pollutant removal action is diminished. In addition, these vinyl-based or polyamide-based water-soluble synthetic polymers may exhibit a thixotropic phenomenon, which is unsuitable as a product for use in the present invention.

As the surfactant used in the present invention, either an ionic surfactant (anionic type, cationic type or zwitterionic type) or a nonionic surfactant can be used, but the composition of the present invention is prepared. Since high-speed stirring is usually employed, glucosides such as saponins and proteins are not preferable from the viewpoint of preventing significant foaming.

Examples of the water-soluble alkali metal salt or alkaline earth metal salt include alkali metals (Li, Na, K, C).
s) or alkaline earth metals (Ca, Mg, Ba, S
Examples of the r) include chlorides, bromides, nitrates, nitrites, borofluorides, and hydrosilicofluorides, and other water-soluble fluorides, silicates, borates, phosphates, sulfates, Organic acid salts and sulfonic acid salts may be used alone or as a mixture. However, if the polysaccharide is previously an alkali salt (eg sodium alginate, sodium carboxymethylcellulose) or the surfactant is an alkali salt (eg sodium alkylsulfate, sodium alkylbenzenesulfonate), these alkali salts Does not have to be counted as a water-soluble alkali metal salt or alkaline earth metal salt, but the impurities (including builders) contained therein are considered to be alkali salts.

The metal component of the water-soluble alkali metal salt or alkaline earth metal salt is the alkali metal ion or alkaline earth metal ion contained therein which is quantitatively analyzed according to a conventional method, and the alkali metal oxide (for example, alkali metal oxide) is analyzed. Na
₂ O, K ₂ O, etc.) or an alkaline earth metal oxide (eg, CaO, MgO, BaO, etc.).

Metal content (as oxide) 0.01 to 3.0
The amount of 0 parts by weight is an amount which is useful for stabilizing the micelle matrix in the thickened liquid-sol-gel of the present invention, and should not be an amount that causes coagulation and precipitation of water-soluble polysaccharides and the like. .. This appropriate amount is 0.
01 to 3.00 parts by weight, particularly preferably 0.07
˜2.50 parts by weight. That is, if it is less than 0.01 parts by weight, the micelle matrix is not stabilized due to fluctuations, and if it is more than 3.00 parts by weight, the micelles in the liquid may be broken to cause phase separation to cause aggregation and precipitation. Confirmed from many experiments.

In the present invention, each of the above components is dispersed or emulsified in water or water-polyol as a solvent, and the appropriate amount is 30 to 70 parts by weight, particularly preferably 40. It was experimentally found to be -60 parts by weight.

Examples of the polyol in this case include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, diglycerin, pentaerythritol, dipentaerythritol, trimethylolpropane, Examples thereof include ethylene propylene glycol, butylene glycol, hexylene glycol, diethanolamine, triethanolamine, and thiodiglycol, which are used as an aqueous solution having 1 to 30% by weight dissolved in water. These polyols can be used for the purpose of delaying the evaporation of water and preventing the fluctuation phenomenon of the micelle matrix.

A suitable inorganic substance may be added in the form of fine powder or sol for the purpose of mechanically increasing the effect of removing contaminants. As the inorganic component, for example, silica,
There are talc, aluminum silicate, clay, kaolin, carbon powder, bentonite, attapulgite, alumina, zirconia, titania, zinc white, barium sulfate, calcium sulfate, iron oxide, calcium carbonate, dolomite, chlorite, hydroapatite and the like. For the same purpose, a small amount of organic filler fine powder such as wood powder, nut shell powder, fibrin powder, leather powder, legume powder, starch, protein powder and coal powder may be contained. However, so as not to impair the interaction of each component and the stability of the formulation, which is a feature of the present invention,
It is preferable to give sufficient consideration to solubility, specific gravity, surface acidity (or basicity), isoelectric point, particle shape, average particle size, oil absorbency, water absorbency, and addition amount.

In producing the composition of the present invention, first, 20 to 60 parts by weight, particularly preferably 25 to 50 parts by weight of a non-conjugated terpene hydrocarbon represented by the above composition formula C ₁₀ H ₁₆ is first added. Dispersed in water or a water-polyol mixture under high speed stirring in an emulsion in the presence of 0.5 to 30.0 parts by weight of surfactant, particularly preferably 0.7 to 20.0 parts by weight,
The above water-soluble polysaccharide 0.5-5.0
Parts by weight, particularly preferably 1.0 to 4.0 parts by weight, are mixed with dissolved water and a water-polyol mixture.

This mixing is carried out under high speed stirring (for example, 500 to
5,000 rpm). Addition of water-soluble alkali metal salt or alkaline earth metal salt (often made into an aqueous solution in advance) is a solution of water-soluble polysaccharide, a solution containing a surfactant, or an emulsion dispersion containing all of them. Add to either of the liquids at one time or in small portions, and stir vigorously at the end. To prepare a concentrated aqueous solution of a water-soluble polysaccharide, dissolution and stirring are carried out at room temperature to 100 ° C., particularly preferably 30 to 90 ° C., but addition of an emulsion of a terpene hydrocarbon to this solution is In most cases 70 ° C or lower, particularly preferably 6
It is allowed to cool after being performed at 0 ° C or lower.

During this cooling, the formation of micelles and dispersion of fine particles with terpene hydrocarbons were achieved, and soap-like, edible konjak-like, jelly-like, cream-like, or dressing was obtained. Includes items with similar hardness. The form from these semi-solids to fluids can be selected according to the purpose of use.

The present inventors have conducted many studies on the quantitative relationship of each component, particularly the relationship between this and the stability and use of the product, and as a result, the composition of the present invention was finally provided to the market. It was found that the form can be determined in a very wide range. For example, stick-like solids, gels in plastics containers, gels in metal cans, sols in plastic bags, sols in metal tubes, sols in plastics tubes, creams in plastics bags It can be in the form of a paste, a cream containing a metal tube, a cream containing a plastic tube, a cream containing a bottle, or a dressing for spraying. The product of the present invention is extremely easy to use because it can be rubbed on the contaminants and then rubbed with a paper, cloth or mop to remove the contaminants.

[0023]

The present inventors have conducted many experiments on the present invention and clarified the superiority of the present invention. In order to further explain the technical contents of the present invention, representative ones will be described below. It will be shown as an example. Therefore, the present invention should not be construed as being limited to the examples shown below, and it goes without saying that the embodiments can be arbitrarily modified and implemented without departing from the spirit and the spirit of the present invention. Is.

[0024]

Example 1 19 g of carrageenan, 5 g of sodium carboxymethyl starch and 1 g of guar gum were added to 300 ml of purified water, heated to 85 ° C., and stirred at high speed (2, 2).
(00 rpm) to dissolve and use this as solution (A).

25 g of nonylphenol ethylene oxide / propylene oxide adduct and 5 g of sodium dodecylbenzene sulfonate were dissolved in 300 ml of purified water,
320 g of limonene was added to this aqueous solution, and high speed stirring (70
0 rpm) to completely emulsify and use this as solution (B).

The liquid (A) is cooled to 60 ° C., the liquid (B) is added thereto, and high speed stirring (2,000 to 3,000 r) is performed.
pm), a saturated aqueous solution containing 4 g of potassium chloride is added, and when the whole becomes uniform, it is left for a while and then poured into a plastics frame mold and cooled to 10 ° C. to be molded. This molded product was a white konjak-like gel and was well cleaned when it was used for cleaning metal products with magic ink, tar and pitch.

[0027]

Example 2 The same treatment as in Example 1 was carried out using an aqueous solution containing 30% of diglycerin instead of the purified water of the solution (B). A slightly elastic gel was obtained, which was filled in an empty case for lipstick. It is mainly used for erasing magic ink. After rubbing the magic ink coating with this stick and wiping it off with a tissue paper, the ink on the metal surface, plastic surface, marble surface, rubber surface or ceramic surface was removed.

[0028]

Example 3 6.0 g of gellan gum in 300 g of purified water,
0.5 g of sodium carboxymethyl cellulose and 0.2 g of dextrin were added and high speed stirring (2,000 rp
m), and heating to 90 ° C. to dissolve, and this is designated as solution (A).

On the other hand, 300 g of dipentene was emulsified in 350 ml of an aqueous solution containing 10% glycerin with 3.0 g of sodium dodecyl sulfate and 1.0 g of potassium chloride to obtain a liquid (B).

After the liquid (A) and the liquid (B) were stirred at high speed (1,600 rpm) at 50 to 60 ° C. and poured into a plastic container, a soft soapy and elastic gel was obtained. .. This product was most suitable for removing contaminants such as adhesive residue and Alfart deposits from automobile parts, and was also excellent for removing stains on printing equipment and polyurethane floors. It can also be applied to remove stains on textiles.

[0031]

Example 4 0.5 g of sodium carboxymethyl cellulose and 0.2 locust bean gum in 40 ml of distilled water.
g and 0.3 g of gum arabic are dissolved at room temperature to obtain a solution (A).

On the other hand, 6 g of sodium lauryl sulfate, 0.5 g of sodium sulfate and 30 g of β-terpinene were dispersed in 30 ml of distilled water to prepare a liquid (B).

After adding (B) liquid and 3.0 g of Aerosil silica to the (A) liquid and performing high speed stirring (2,000 rpm), the mixture sol is filled in a plastic stube. This gelled product is in the form of paste gel and is extruded from a tube to be used for decontamination of molded plastics and films. Polyethylene terephthalate, polyamide, polybutylene terephthalate, ABS resin, polyethylene, polypropylene, polycarbonate, (meth)
It was possible to effectively remove oils, hand marks, fingerprints, etc. adhering to the acrylate resin plate. It was also used to clean oily skin.

[0034]

Example 5 In 350 ml of distilled water, 5 g of hydroxypropyl cellulose and 5 g of Zalep mannan were dissolved by high-speed stirring (1,500 rpm), and 8 g of aerosil alumina was added to the solution to further disperse it. ) Use as liquid.

On the other hand, 100 g of a 50% solution of benzethonium chloride in a pharmacopoeia and 100 g of a 50% solution of benzalkonium chloride in a pharmacopoeia were dissolved by stirring in 300 ml of distilled water, and this was dissolved in (B).
Use as liquid.

Then, the solution (B) is rapidly stirred at room temperature (1,0
Orange peel oil (d-limonene 9)
200 g (containing 0%) and lemon peel oil (d-limonene 87)
% Of 100%) was gradually added to emulsify the mixture, and then the mixture of (A) heated to 50 ° C. and 5 g of calcium nitrite were added thereto, and high-speed stirring (2,500 rpm) was performed to obtain a coating with very good aromaticity. An easy paste sol was obtained. Since this one has a contaminant removing property and a bactericidal effect,
It was used for cleaning walls and equipment such as tatami mats, conference halls, trains, station buildings, hospitals, etc. When used actually, cleaning was achieved well.

[0037]

Examples 6 to 10 and Comparative Examples 1 to 5 Limonene 50
g, sodium lauryl sulfate 5 g, potassium chloride 1.0
g to 50 g of purified water and sufficiently stirred to emulsify, which is used as solution (A).

On the other hand, 4 g of the water-soluble polymer shown in Table 1 was added to 50 g of purified water, mixed well and mixed at 50-60 ° C. (B).
Prepare the liquid. High speed stirring of (B) liquid (1,800 r
(A) while adding the solution (A) and cooling after 20 minutes. Table 1 shows the results of examining the action of removing the coating material of the oil-based ink from the sol to gelled product obtained here. The evaluation criteria are as follows. The removal work is the same as in the second embodiment. ◎: Excellent ○: Good △: Acceptable ×: Impossible

[0039]

[Table 1]

[0040]

Examples 12 to 17 and Comparative Examples 6 to 10 Examples 6 to
In 11, the cases of adding the predetermined components shown in Table 2 in place of potassium chloride and the case of not adding were investigated. The results are shown in Table 2.

[0041]

[Table 2]

[0042]

Examples 18 to 21 and Comparative Examples 11 to 15 Distilled water 3
To 00 g, 6.0 g of gellan gum powder, 0.4 g of sodium carboxymethyl cellulose and 0.0 g of guar gum.
While adding 3 g and stirring at high speed (2,000 rpm),
It is heated to 5 ° C. to dissolve it, and this is designated as solution (A).

On the other hand, 300 g of a predetermined terpene hydrocarbon having a composition of C ₁₀ H ₁₆ shown in Table 3, 3.0 g of sodium dodecylbenzenesulfonate, 0.7 g of potassium chloride and 0.7 g of calcium chloride were added to 400 g of distilled water. Then, the mixture is stirred and emulsified to prepare the liquid (B).

The liquid (A) and the liquid (B) are mixed at 50 to 60 ° C.
The mixture is stirred at 2,000 rpm for 30 seconds, poured into an aluminum container and cooled to form a gel. A slice of this gel having a thickness of about 2 mm is placed on a chewing gum-adhered iron plate, left at room temperature for 1 hour, and then wiped with a cotton cloth. The results are shown in Table 3. The evaluation of the degree of gum removal is indicated by ⊚, ○, Δ, and × marks. The evaluation criteria are Examples 6 to 10 and Comparative Examples 1 to 1.
5 is the same as Table 1.

[0045]

INDUSTRIAL APPLICABILITY The present invention relates to a composition for removing contaminants and a method for producing the same, which is a mucus for removing various contaminants from oil-based inks, oils or gums to adhesives and the like. ~ Sol ~ It relates to the commercialization of a new composition in solid form. With the completion of the present invention, a wide range of applications from daily commodities to industrial products are expected, and it can be said that the effects of the present invention on industry are tremendous.

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Fujinaga Matsunaga 2-10-8 Sekido, Wakayama, Wakayama (72) Inventor Hiroomi Kamon 426-45 Kisendai, Iwade-cho, Naga-gun, Wakayama (72) Invention Hiroshi Ehara 277-801 Nagayama, Kishikawa-cho, Naga-gun, Wakayama Prefecture (72) Inventor Yoshifumi Matsuda 311 Nishino, Naga-cho, Naga-gun, Wakayama Prefecture (72) Inventor Kazuhide Momoi 3-39 Usu, Wakayama City, Wakayama Prefecture (72) Inventor Masahiro Matsuda 149-38 Nakatsu, Kakogawa-cho, Kakogawa-shi, Hyogo (72) Inventor Nao Kitano 3-1-2, Harima-cho, Abeno-ku, Osaka-shi, Osaka

Claims (2)

[Claims] 1. A terpene-based hydrocarbon having two non-conjugated double bonds represented by a composition formula of C ₁₀ H ₁₆ in an amount of 20 to 60 parts by weight and a water-soluble polysaccharide in an amount of 0.5 to 5.0 parts by weight, Surfactant 0.5 to 30.0 parts by weight, metal component of water-soluble alkali metal salt or alkaline earth metal salt (as oxide)
A contaminant-removing composition comprising 0.01 to 3.00 parts by weight and 30 to 70 parts by weight of water or a water-polyol mixture. 2. 20 to 60 parts by weight of a terpene-based hydrocarbon having two non-conjugated double bonds represented by a composition formula of C ₁₀ H ₁₆ and 0.5 to 30.0 parts by weight of a surfactant. After being dispersed in water or a water-polyol mixture in the presence of water, the solution is added to a solution of water or a water-polyol mixture in which 0.5 to 5.0 parts by weight of the water-soluble polysaccharide is dissolved, and a water-soluble alkali metal salt or alkaline earth is added. A method for producing a contaminant-removing composition, which comprises thickening or gelling in the presence of 0.01 to 3.00 parts by weight of a metal component (as an oxide) of a metal salt.